A density functional theoretical (DFT) study is presented, implicating a O oxidation process to reach a dihydrobenzofuran from the reaction of the natural homoallylic alcohol, glycocitrine. Our results predict an interconversion between glycocitrine and an iso-hydroperoxide intermediate [R(H)O -O ] that provides a key path in the chemistry which then follows. Formations of allylic hydroperoxides are unlikely from a O 'ene' reaction. Instead, the dihydrobenzofuran arises by O oxidation facilitated by a 16° curvature of the glycocitrine ring imposed by a pyramidal N-methyl group. This curvature facilitates the formation of the iso-hydroperoxide, which is analogous to the iso species CH I -I and CHI -I formed by UV photolysis of CH I and CHI . The iso-hydroperoxide is also structurally reminiscent of carbonyl oxides (R C=O -O ) formed in the reaction of carbenes and oxygen. Our DFT results point to intermolecular process, in which the iso-hydroperoxide's fate relates to O-transfer and H O dehydration reactions for new insight into the biosynthesis of dihydrobenzofuran natural products.
Download full-text PDF |
Source |
|---|---|
| http://dx.doi.org/10.1111/php.13843 | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
A General Three-Component Nozaki-Hiyama-Kishi-Type Reaction Enabled by Delayed Radical-Polar Crossover.
J Am Chem Soc
January 2025
Organisch-Chemisches Institut, Universität Münster, Münster 48149, Germany.
Nozaki-Hiyama-Kishi (NHK) reactions offer a mild approach for the formation of alcohol motifs through radical-polar crossover-based pathways from various radical precursors. However, the application of multicomponent NHK-type reactions, which allow the formation of multiple bonds in a single step, has been largely restricted to bulky alkyl radical precursors, thus limiting their expanded utilization. Herein, we disclose a general three-component NHK-type reaction enabled by delayed radical-polar crossover, which efficiently tolerates a plethora of radical precursors that were previously unavailable.
View Article and Find Full Text PDFHighly Stereo- and Enantioselective Syntheses of δ-Alkyl-Substituted ()-Homoallylic Alcohols.
Org Lett
January 2025
Department of Chemistry, Virginia Tech, Blacksburg, Virginia 24061, United States.
Highly stereo- and enantioselective synthesis of δ-alkyl-substituted ()-homoallylic alcohols via asymmetric allylation is developed. In the presence of a chiral phosphoric acid catalyst, allylation of aldehydes with α-substituted allylboronates provides δ-alkyl-substituted homoallylic alcohols with excellent ()-selectivities and enantioselectivities.
View Article and Find Full Text PDFBiomimetic Catalytic Remote Desaturation of Aliphatic Alcohols.
Org Lett
January 2025
Leibniz Institute for Catalysis e.V., Albert-Einstein-Str. 29a, 18059 Rostock, Germany.
Herein we present photoinduced cobaloxime-catalyzed selective remote desaturation of aliphatic alcohols. This transformation, which proceeds efficiently at room temperature, facilitates the synthesis of valuable cyclic and acyclic allylic and homoallylic alcohols from readily available saturated aliphatic alcohols. Remarkably, this method obviates the need for external oxidants, noble metal catalysts, and phosphine ligands.
View Article and Find Full Text PDFNickel Photoredox/Dual-Catalyzed Transfer Semi-Hydrogenation of Alkynes via Aminoalkyl Nickel Species.
J Org Chem
January 2025
Faculty of Pharmaceutical Sciences, Hokkaido University, Sapporo 060-0812, Japan.
Using amines in catalytic transfer hydrogenation (TH) is challenging, despite their potential availability as a hydrogen source. Here, we describe a photoredox/nickel-catalyzed TH of alkyne through an intermediary aminoalkyl Ni species. This reaction successfully provided functionalized ()-alkenes, such as (homo)allyl ethers, alcohols, and amides (/ = up to >99:1), and the reaction thus bypasses a limitation of substrate scope in TH using amine and a Lindlar catalyst.
View Article and Find Full Text PDFPhotochemical carboborylation and three-component difunctionalization of α,β-unsaturated ketones with boronic acids tosylhydrazones.
Chem Sci
November 2024
Departamento de Química Orgánica e Inorgánica, Instituto Universitario de Química Organometálica "Enrique Moles", Instituto de Investigación Sanitaria del Principado de Asturias (ISPA), Centro de Innovación en Química Avanzada (ORFEO-CINQA), Universidad de Oviedo C/ Julián Clavería 8 33006 Oviedo Spain
The reactions of cyclic α,β-unsaturated -tosylhydrazones and alkylboronic acids promoted by 370-390 nm light in the presence of a base give rise to allylic boronic acids that can be trapped as the corresponding pinacolboronates by treatment with pinacol. This reaction features wide scope regarding both coupling partners and functional group tolerance, allowing for the incorporation of a variety of natural product-derived fragments. The allylic boronic acids can be also reacted in a one-pot process with aldehydes, to produce homoallylic alcohols with very high diastereoselectivity.
View Article and Find Full Text PDFWant AI Summaries of new PubMed Abstracts delivered to your In-box?
Enter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!